CN117504579A - SCR denitration system taking CO as reducing agent, application of SCR denitration system and SCR denitration method - Google Patents
SCR denitration system taking CO as reducing agent, application of SCR denitration system and SCR denitration method Download PDFInfo
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- CN117504579A CN117504579A CN202311508800.XA CN202311508800A CN117504579A CN 117504579 A CN117504579 A CN 117504579A CN 202311508800 A CN202311508800 A CN 202311508800A CN 117504579 A CN117504579 A CN 117504579A
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- 239000003638 chemical reducing agent Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 89
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000003546 flue gas Substances 0.000 claims abstract description 47
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 230000009467 reduction Effects 0.000 claims description 25
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 230000002378 acidificating effect Effects 0.000 claims description 19
- 238000006477 desulfuration reaction Methods 0.000 claims description 15
- 230000023556 desulfurization Effects 0.000 claims description 15
- 239000000428 dust Substances 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 7
- 239000000969 carrier Substances 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 230000009849 deactivation Effects 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000007789 gas Substances 0.000 description 12
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 12
- 238000011068 loading method Methods 0.000 description 10
- 230000003213 activating effect Effects 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 229910004298 SiO 2 Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007086 side reaction Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000003009 desulfurizing effect Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- AZLYZRGJCVQKKK-UHFFFAOYSA-N dioxohydrazine Chemical compound O=NN=O AZLYZRGJCVQKKK-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- -1 tiO 2 Inorganic materials 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8631—Processes characterised by a specific device
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
- B01D53/8628—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/90—Injecting reactants
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Exhaust Gas Treatment By Means Of Catalyst (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an SCR denitration system taking CO as a reducing agent, application thereof and an SCR denitration method, belonging to the technical field of flue gas purification, wherein the SCR denitration system comprises: the SCR denitration reactor comprises a reduction-storage double-layer catalyst and is distributed at intervals in multiple rings. The invention also discloses a method for removing NO from industrial flue gas with high CO/NO ratio under the condition of oxygen content by using the SCR denitration system x Is used in the field of applications. Meanwhile, an SCR denitration method using CO as a reducing agent is disclosed, and the SCR denitration system using CO as the reducing agent is used. The method and the system provided by the invention can remarkably improve the deactivation problem of the CO-SCR denitration catalyst under the condition of oxygen content, and can be used in the industry with high CO/NO ratioThe field of flue gas purification has wide application prospect. In addition, the heating temperature of the hot blast stove is lower than that of the conventional NH 3 The SCR denitration device has good economy and is easy for industrial application.
Description
Technical Field
The invention belongs to the technical field of flue gas purification, and particularly relates to an SCR denitration system taking CO as a reducing agent, application of the SCR denitration system and an SCR denitration method.
Background
Selective Catalytic Reduction (SCR) technology is currently the dominant solution for industrial flue gas denitrification. Typical reductant ammonia (NH) 3 ) Besides increasing the cost of denitration technology, the introduction of the method can also corrode equipment to make the flue gas escape to cause secondary pollution. Due to incomplete combustion, a large amount of CO is commonly present in flue gas of an industrial furnace, wherein CO is a reducing gas with high heat value and belongs to one of environmental air quality monitoring pollutants. CO instead of NH 3 The catalytic denitration can reduce the energy consumption of an external reducing agent, avoid the pollution risk of ammonia escape and realize the simultaneous removal of pollutants, and is a denitration technology with application prospect of treating waste with waste.
However, high-concentration oxygen in industrial flue gas has a remarkable inhibition effect on CO catalytic denitration, and on one hand, the oxygen reacts with CO and consumes a reducing agent; on the other hand, the oxygen reacts with NO to generate NO 2 Byproducts. Mainly relates to the following three reaction processes:
2NO+2CO→N 2 +2CO 2 (Main)
2CO+O 2 →2CO 2 (auxiliary)
2NO+O 2 →2NO 2 (auxiliary)
Wherein CO is oxidized to CO 2 Is an exothermic process, and can play a role in supplementing heat to the flue gas and improving the denitration efficiency. Thermodynamically, CO reduces NO 2 (Δg= -1109.74kj,120 ℃) more readily occurs than directly reducing NO (Δg= -668.66kj,120 ℃). Thus NO 2 The secondary decomposition of the byproducts can be promoted by timely capturing. Catalytic reduction of NO compared to CO x The reaction can occur under the Eley-Rideal mechanism (NO adsorption, CO non-adsorption), and CO adsorption on the material surface is a key step in CO oxidation reaction. Once other gas components in the flue gas poison the adsorption sites of CO in advance, the occurrence of CO oxidation side reaction can be reduced.
Therefore, how to provide an SCR denitration method and system using CO as a reducing agent capable of capturing materials is a technical problem that needs to be solved by those skilled in the art.
Disclosure of Invention
In order to solve the technical problems, the invention provides an SCR denitration system taking CO as a reducing agent, application of the SCR denitration system and an SCR denitration method, and solves the problem that the CO-SCR technology is difficult to apply in high-oxygen-concentration industrial flue gas.
In order to achieve the above purpose, the present invention provides the following technical solutions:
an SCR denitration system using CO as a reducing agent, comprising: the SCR denitration reactor comprises a reduction-storage double-layer catalyst and is distributed at intervals in multiple rings.
Preferably, the SCR denitration system comprises a dust remover, a hot blast stove, the SCR denitration reactor, a desulfurization device and a chimney which are connected in sequence;
preferably, the SCR denitration reactor belongs to a fixed bed device, and comprises a multi-ring catalyst layer inside, and is formed by sequentially assembling a rectifying layer, a multi-ring catalyst layer and an ash bucket from top to bottom;
the number of the multi-ring catalyst layers is 2-4;
the reduction-storage double-layer catalyst consists of a multi-ring interval filling reduction catalyst and a storage catalyst in the multi-ring catalyst layer;
the polycyclic catalyst layer comprises 5-9 rings, preferably 5, 7, 9 rings;
the mass ratio of the reduction catalyst to the storage catalyst is 5:1-10:1, preferably 5:1, 7: 1. 10:1.
The beneficial effects are that: the invention adopts a reduction-storage double-layer catalyst, NO and CO and O on the surface of the reduction catalyst 2 Reaction to produce N 2 And NO 2 ，NO 2 Then overflows to the surface of the stored catalyst and reacts with CO for the second time to generate N 2 ；
The working principle of the SCR denitration reactor provided by the invention comprises the following steps:
(1) NO is stillProcatalyst surface with CO and O 2 Reaction to produce N 2 And NO 2 ；
Wherein the chemical reaction includes, but is not limited to, the following:
NO(g)→NO(ads)；
NO(ads)+NO(ads)→ONNO(ads)；
ONNO(ads)+CO(g)→ONN(ads)+CO 2 (g)；
ONN(ads)+CO(g)→N 2 (ads)+CO 2 (g)；
N 2 (ads)→N 2 (g)；
NO(ads)+2O * →NO 3 - (ads)；
NO 3 - (ads)+CO(g)→NO 2 (ads)+CO 2 (g)；
NO 2 (ads)→NO 2 (g)；
(2)NO 2 then overflows to the surface of the stored catalyst and reacts with CO for the second time to generate N 2 ；
Among them, chemical reactions include, but are not limited to, the following:
NO 2 (g)→NO 2 (ads)；
MO+NO 2 (ads)→MNO 3 (ads) (M is a metal ion);
2MNO 3 (ads)+4CO(g)→2MO+N 2 (ads)+4CO 2 (g)；
N 2 (ads)→N 2 (g)。
the ratio of CO to NO in the step (1) and the step (2) is 10-200, preferably 10, 50, 100, 150 and 200;
O 2 the concentration is 5-16%, preferably 6%, 10%, 16%;
the reaction temperature is 220-320 ℃, such as 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃, 320 ℃.
Preferably, the catalyst in the reduction catalyst layer includes a support, an acidic metal, and an active component, wherein the acidic metal is supported on the support, and the active component is supported on the acidic metal.
Preferably, the active component comprises any one or a combination of a plurality of Ir-based, pt-based, ag-based, au-based, ru-based, pd-based and Rh-based components;
more preferably, the active component comprises IrO 2 、IrCl 3 、PtO 2 、PtCl 4 、Ag 2 O、AgCl、Au 2 O 3 、AuCl 3 、RuO 2 、RuCl 3 、PdO、PdCl 2 、RhO 2 、RhCl 3 One or a combination of both;
the acidic metal comprises any one or a combination of a plurality of W-based acidic metals, mo-based acidic metals and Nb-based acidic metals;
more preferably, the acidic metal comprises WO 3 、WCl 6 、MoO 3 、MoCl 5 、Nb 2 O 5 、NbCl 5 One or a combination of both;
the carrier comprises any one or a combination of a plurality of Al-based, si-based, ti-based, ce-based and Co-based carriers.
More preferably, the carrier comprises Al 2 O 3 、SiO 2 Molecular sieve, tiO 2 、CeO 2 、Co 3 O 4 One or a combination of both;
preferably, the active ingredient loading is 0.02 to 1wt.%;
the acidic metal loading is 3-7wt.%;
the carrier has particle diameter of 5-100nm and specific surface area of 100-500m 2 /g。
More preferably, the surface of the reduction catalyst contains abundant hydroxyl groups;
the surface of the reduction catalyst is rich in hydroxyl groups caused by unsaturated coordination of partial atoms on the surface of the catalyst, the content of the hydroxyl groups is related to the specific surface area, and the hydroxyl groups can be controlled by morphology and crystal faces.
The hydroxyl group comprises any one or a combination of a plurality of terminal hydroxyl groups, bridged hydroxyl groups and three-coordination hydroxyl groups.
The hydroxyl groups are mainly terminal hydroxyl groups, and the content of the terminal hydroxyl groups is preferably more than 60% of the number of the hydroxyl groups.
More preferably, the reduction catalyst comprises Ir-W/TiO 2 Catalyst, pt-W/TiO 2 Catalyst or Ir-W/CeO 2 One of the catalysts had an Ir or Pt loading of 0.5wt.%, a W loading of 5wt.%, the remainder being the support.
Preferably, the reduction catalyst is activated by an activating gas before use;
the activating gas comprises H 2 CO and NH 3 Any one or a combination of a plurality of the above;
the activation time is 0.5-2h, preferably 0.5h, 1h, 1.5h, 2h;
the activation temperature is 200-400 ℃, preferably 200 ℃, 300 ℃ and 400 ℃;
the activated gas concentration is 5% -10%, preferably 5%, 8%, 10%.
The activation treatment specifically comprises the following steps:
and (3) putting a certain amount of catalyst into a tubular furnace, introducing activating gas at the gas flow rate of 100ml/min, heating the tubular furnace to the activating temperature at the speed of 10 ℃/min after 1h, cooling under the same atmosphere after the activating time is reached, stopping introducing the activating gas after cooling to the room temperature, and taking out the catalyst.
Preferably, the storage catalyst comprises a storage component and a carrier, and the storage component is supported on the carrier;
the storage component comprises any one or a combination of a plurality of Ba base and K base;
more preferably, the storage component comprises BaO, ba (HCO) 3 ) 2 、BaCO 3 、KHCO 3 、K 2 CO 3 One or a combination of several of them;
the carrier comprises any one or a combination of a plurality of Al-based, si-based, ti-based, ce-based and Co-based.
More preferably, the carrier comprises Al 2 O 3 、SiO 2 Molecular sieve, tiO 2 、CeO 2 、Co 3 O 4 One or a combination of several of them；
Preferably, the storage component is present on the support at a loading of 10 to 40wt.%;
the particle diameter of the carrier is 100nm-10 μm, and the specific surface area is 50-20m 2 /g。
More preferably, the storage catalyst comprises Ba/Al 2 O 3 The catalyst, ba loading was 10wt.%, the remainder being the support.
The desulfurization device is one or a combination of at least two of a circulating fluidized bed semi-dry desulfurization device, a rotary spray semi-dry desulfurization device and a wet desulfurization device.
The beneficial effects are that: the system provided by the invention has the advantages that the desulfurization device is arranged behind the SCR denitration reactor, and pollutants SO in the flue gas are fully utilized 2 The method comprises the steps of carrying out a first treatment on the surface of the By means of annular interval arrangement design, the synergistic effect between the reducing catalyst and the storing catalyst is fully developed.
SCR denitration system taking CO as reducing agent removes NO from industrial flue gas with high CO/NO ratio under oxygen-containing condition x Is used in the field of applications.
Preferably, the concentration ratio of CO to NO in the industrial flue gas is 10-200:1, preferably 10:1, 50:1, 100:1, 150:1, 200:1.
More preferably, O in the industrial flue gas 2 The concentration is 5-16%;
more preferably, the industrial flue gas with high CO/NO ratio is flue gas of a coal-fired power plant, steel sintering flue gas and the like.
An SCR denitration method using CO as a reducing agent uses the SCR denitration system using CO as the reducing agent.
Preferably, the method comprises the following steps:
and (3) introducing industrial flue gas into a dust remover, sequentially passing through a hot blast stove, an SCR denitration reactor and a desulfurization device, and finally discharging the treated flue gas through a chimney to finish SCR denitration of the flue gas.
More preferably, the method specifically comprises the following steps:
(1) Industrial flue gas enters the hot blast stove from the top outlet of the dust remover, the industrial flue gas is heated after passing through the hot blast stove, and then the industrial flue gas is heated from the hot blast stoveThe lateral outlet enters the SCR denitration reactor and then passes through the rectifying layer and the catalyst layer from top to bottom, wherein the industrial flue gas is more uniform after passing through the rectifying layer, and N is generated after the catalyst layer reacts with the reduction-storage double-layer catalyst for multiple times 2 And CO 2 ；
(2) And after the reaction is finished, the industrial flue gas enters a desulfurization device from an outlet at the bottom of the SCR denitration reactor, and the desulfurized flue gas enters a chimney after reaching the emission standard.
More preferably, the stove heats the flue gas to 200-300 ℃, preferably 200 ℃, 220 ℃, 240 ℃, 260 ℃, 280 ℃, 300 ℃;
inlet SO of the SCR denitration reactor 2 The concentration is 35-1000mg/m 3 ；
The working temperature of the multi-layer catalyst layer in the SCR denitration reactor is 220-320 ℃;
the space velocity of the multi-layer catalyst layer for industrial flue gas treatment is 15000-60000h -1 Preferably 15000h -1 、30000h -1 、45000h -1 、60000h -1 。
The beneficial effects are that: the SCR denitration method provided by the invention utilizes CO oxidation heat release to heat the flue gas, so that the heat supplementing energy consumption of a part of hot blast stoves is reduced; promotion of SO with acidic metals 2 Adsorbing on the surface of the reduction catalyst, thereby inhibiting the CO oxidation side reaction of the reducing agent; rapid NO capture using storage catalysts 2 By-products, thereby promoting their secondary decomposition.
The invention provides an SCR denitration system taking CO as a reducing agent, application thereof and an SCR denitration method, firstly, the reduction catalyst comprises acidic metal and can promote SO 2 Adsorbing and oxidizing on the surface of the reduction catalyst, thereby occupying CO adsorption sites and inhibiting CO oxidation side reaction. The NO conversion efficiency is improved under the oxygen-containing condition. Secondly, the reduction-storage double-layer catalysts are arranged at intervals, and NO is rapidly captured by utilizing the overflow effect of gas between the double-layer catalysts 2 By-product, promoting its secondary decomposition, and increasing N under oxygen-containing condition 2 Selectivity. The method and the system provided by the invention can be obviously improvedDeactivation of CO-SCR denitration catalyst under oxygen-containing condition, irWSiO 2 Catalyst at 5% O 2 Lower NO x The removal efficiency reaches 85 percent, and has wide application prospect in the field of industrial flue gas purification with high CO/NO ratio. In addition, the denitration system provided by the invention has the advantages that the heating temperature of the hot blast stove is lower than that of the conventional NH 3 The SCR denitration device has good economy and is easy for industrial application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application, illustrate and explain the application and are not to be construed as limiting the application. In the drawings:
fig. 1 is a schematic structural connection diagram of an SCR denitration system using CO as a reducing agent according to embodiment 1 of the present invention.
1, a dust remover; 2. hot blast stove; 3. an SCR denitration reactor; 4. a rectifying layer; 5. a multi-ring catalyst layer; 6. an ash bucket; 7. a reduction catalyst; 8. storing the catalyst; 9. a desulfurizing device; 10. and (5) a chimney. Wherein the solid arrows represent the flow direction of the flue gas.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In order that the above-recited objects, features and advantages of the present invention will become more readily apparent, a more particular description of the invention will be rendered by reference to the appended drawings and appended detailed description.
In the embodiment of the invention, the treatment industrial smoke volume is 200000Nm 3 And/h, the concentration of NO in the industrial flue gas is 400ppm, the concentration of CO is 8000ppm, and the concentration of O is 2 The concentration was 5% and the industrial flue gas temperature was 120 ℃.
Example 1
An SCR denitration system using CO as a reducing agent, as shown in figure 1, comprises a dust remover 1, a hot blast stove 2, an SCR denitration reactor 3, a desulfurization device 9 and a chimney 10 which are sequentially connected.
Specifically, the top outlet of the dust remover 1 is communicated with the bottom inlet of the hot blast stove 2, the lateral outlet of the hot blast stove 2 is communicated with the top inlet of the SCR denitration reactor 3, the bottom outlet of the SCR denitration reactor 3 is connected with the bottom inlet of the desulfurizing device 9, and the top outlet of the desulfurizing device 9 is connected with the bottom inlet of the chimney 10.
The SCR denitration reactor 3 belongs to a fixed bed device and is formed by sequentially connecting a rectifying layer 4, 3 layers of multi-ring catalyst layers 5 and an ash bucket 6. The reduction catalyst and the storage catalyst on the catalyst layer are distributed at intervals of multiple rings. The reduction catalyst is Ir-W/SiO 2 Catalyst, ir loading of 0.5wt.%, W loading of 5wt.%, balance SiO 2 A carrier; the storage catalyst is Ba/Al 2 O 3 The catalyst has a Ba loading of 10wt.% and the rest is a carrier; the mass ratio of the reduction catalyst to the storage catalyst is 10:1;
before the reduction catalyst is used, activating treatment is carried out by using activating gas;
the activation treatment specifically comprises the following steps:
taking a certain amount of catalyst, placing into a tube furnace, and introducing 5%H at a gas flow rate of 100ml/min 2 Activating gas, heating the tube furnace to 400 ℃ at 10 ℃/min after 1H, cooling under the same atmosphere after 0.5H of activation, and stopping introducing H after the temperature reaches room temperature 2 The catalyst was removed.
The desulfurization device is a circulating fluidized bed semi-dry desulfurization device.
An SCR denitration method using CO as a reducing agent, which uses the SCR denitration system, specifically comprises the following steps:
(1) Industrial flue gas enters the hot blast stove from the top outlet of the dust remover, the temperature of the industrial flue gas is raised to 200 ℃ after passing through the hot blast stove, and then enters the SCR denitration reactor from the lateral outlet of the hot blast stove, wherein the temperature of the flue gas at the inlet of the SCR denitration reactor is 250 ℃, and then passes through the rectifying layer and the catalyst layer from top to bottom.
Wherein, the space velocity of the denitration reaction is 15000h -1 The method comprises the steps of carrying out a first treatment on the surface of the Industrial flue gas is subjected to treatmentThe flow layer is more uniform, and N is generated after the catalyst layer reacts with the reduction-storage double-layer catalyst for a plurality of times 2 And CO 2 ；
(2) And (3) allowing the industrial flue gas after the reaction to enter a desulfurization device from an outlet at the bottom of the SCR denitration reactor, and allowing the desulfurized flue gas to enter a chimney after reaching the emission standard. Final NO x The removal effect is 85%.
Example 2
An SCR denitration system using CO as a reducing agent differs from example 1 only in that the carrier in the reduction catalyst is changed to CeO 2 I.e. the reduction catalyst is Ir-W/CeO 2 The catalyst, other conditions were identical to those of example 1, giving NO x The removal effect is 75%.
Example 3
An SCR denitration system using CO as a reducing agent differs from example 1 only in that the active component in the reduction catalyst is changed to Pt, i.e., the reduction catalyst is Pt-W/CeO 2 The catalyst, SCR denitration reactor inlet flue gas temperature is 230 ℃, other conditions are the same as those of example 1, and NO is obtained x The removal effect is 80%.
Comparative example 1
An SCR denitration system using CO as a reducing agent is different from example 1 only in that the amount of a storage catalyst is changed to 0g, and other conditions are exactly the same as those of example 1, and in this embodiment, NO as a byproduct is captured in time due to the lack of the storage reducing agent 2 Resulting in the desired product N 2 The yield of (2) was significantly reduced as compared with example 1, and NO was calculated x The removal effect is only 30%.
Comparative example 2
An SCR denitration system using CO as a reducing agent is different from example 1 only in that a desulfurization device is placed before an SCR denitration reactor, i.e., industrial flue gas enters the SCR denitration reactor after passing through a dust remover, a hot blast stove and a desulfurization device, and other conditions are exactly the same as those of example 1, and the SO at the inlet of the SCR denitration reactor in this example 2 The concentration is low, the CO oxidation side reaction is obvious, and the denitration reaction lacks enough reducing agent, so that NO is obtained x The removal effect is only40％。
Comparative example 3
An SCR denitration system using CO as a reducing agent is different from example 1 only in that the acidic metal loading amount in the reduction catalyst is changed to 0wt.%, and other conditions are exactly the same as those of example 1, and this example lacks NO adsorption-dissociation sites, thus obtaining NO x The removal effect is only 16%.
As can be seen from comparison of examples 1-3 and comparative examples 1-3, the SCR denitration method and system using CO as the reducing agent provided by the invention improves the high cost of the reducing agent added in the existing denitration technology and NH through the addition of the acid metal and the synergistic effect between the reduction catalyst and the storage catalyst 3 Escape secondary pollution and the like, and the NO in industrial flue gas is removed by catalysis x Has wide application prospect in the aspect.
The foregoing is merely a preferred embodiment of the present application, but the scope of the present application is not limited thereto, and any changes or substitutions easily conceivable by those skilled in the art within the technical scope of the present application should be covered in the scope of the present application. Therefore, the protection scope of the present application shall be subject to the protection scope of the claims.
Claims (10)
1. An SCR denitration system using CO as a reducing agent, comprising: the SCR denitration reactor is characterized in that the inside of the SCR denitration reactor comprises a reduction-storage double-layer catalyst, and the reduction-storage double-layer catalyst is distributed at intervals in multiple rings.
2. An SCR denitration system using CO as a reducing agent according to claim 1, wherein the inside of the SCR denitration reactor includes a multi-ring catalyst layer;
the reduction-storage double-layer catalyst consists of a reduction catalyst and a storage catalyst which are filled in the multi-ring catalyst layer at intervals;
the multi-ring catalyst layer comprises 5-9 rings;
the mass ratio of the reduction catalyst to the storage catalyst is 5-10:1.
3. The SCR denitration system using CO as a reducing agent according to claim 2, wherein the catalyst in the reduction catalyst layer comprises a carrier, an acidic metal, and an active component, wherein the acidic metal is supported on the carrier, and the active component is supported on the acidic metal.
4. A CO-reductant SCR denitration system according to claim 3, wherein said active component comprises any one or a combination of several of Ir-based, pt-based, ag-based, au-based, ru-based, pd-based and Rh-based components;
the acidic metal comprises any one or a combination of a plurality of W-based acidic metals, mo-based acidic metals and Nb-based acidic metals;
the carrier comprises any one or a combination of a plurality of Al-based, si-based, ti-based, ce-based and Co-based carriers.
5. The SCR denitration system of claim 2, wherein the storage catalyst comprises a storage component and a support, and the storage component is supported on the support.
6. The SCR denitration system using CO as a reducing agent according to claim 5, wherein the storage component comprises any one or a combination of a plurality of Ba groups and K groups;
the carrier comprises any one or a combination of a plurality of Al-based, si-based, ti-based, ce-based and Co-based.
7. An SCR denitration system using CO as reducing agent as defined in any one of claims 1 to 6 for removing NO from industrial flue gas with high CO/NO ratio under oxygen-containing condition x Is used in the field of applications.
8. The use according to claim 8, wherein the concentration ratio of CO to NO is 10-200.
9. An SCR denitration method using CO as a reducing agent, wherein denitration is performed using an SCR denitration system using CO as a reducing agent according to any one of claims 1 to 6.
10. The SCR denitration method as defined in claim 9, wherein the method comprises the steps of:
and (3) introducing industrial flue gas into a dust remover, sequentially passing through a hot blast stove, an SCR denitration reactor and a desulfurization device, and finally discharging the treated flue gas through a chimney to finish SCR denitration of the flue gas.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007205304A (en) * | 2006-02-03 | 2007-08-16 | Hino Motors Ltd | Desulfurization control method for exhaust emission control device |
| CN101422689A (en) * | 2007-11-02 | 2009-05-06 | 中国科学院过程工程研究所 | Flue gas denitration method and device by storing and reducing nitrogen oxides in circulating fluid bed |
| CN101507923A (en) * | 2009-03-24 | 2009-08-19 | 中国科学院过程工程研究所 | Preparation method of catalyst for sintering flue gas and desulfurizing and denitrifying |
| CN101874964A (en) * | 2009-12-11 | 2010-11-03 | 北京科技大学 | Low temperature storage and reduction method for purifying oxynitrides |
| CN102188904A (en) * | 2011-05-11 | 2011-09-21 | 宝钢工程技术集团有限公司 | Denitration system and method for sintering flue gas without ammonia reducing agent |
| CN104667715A (en) * | 2015-02-10 | 2015-06-03 | 南京工业大学 | Flue gas desulfurization and denitrification and dust removal integrated device and process |
| CN104958978A (en) * | 2015-06-10 | 2015-10-07 | 浙江菲达脱硫工程有限公司 | Glass kiln desulfurization, denitration and dust removal apparatus and method thereof |
| CN205073858U (en) * | 2015-10-09 | 2016-03-09 | 广州特种承压设备检测研究院 | DeNOx systems is united with oxidation to reduction |
| CN105457486A (en) * | 2015-11-24 | 2016-04-06 | 西安航天源动力工程有限公司 | Coke oven flue gas integrated treatment method |
| CN106925113A (en) * | 2015-12-29 | 2017-07-07 | 烟台大学 | A kind of dust-removal and desulfurizing denitration flue gas purifying technique |
| CN208356476U (en) * | 2018-05-29 | 2019-01-11 | 北京皓天百能环保工程有限公司 | A kind of low-temperature flue gas redox denitrating system |
| CN109806764A (en) * | 2019-03-25 | 2019-05-28 | 中国科学院过程工程研究所 | A kind of industrial smoke storage reduction denitrating system and method |
| CN113828148A (en) * | 2020-06-23 | 2021-12-24 | 中冶长天国际工程有限责任公司 | Flue gas treatment system and flue gas treatment method for efficiently utilizing carbon monoxide |
| CN114887618A (en) * | 2022-05-10 | 2022-08-12 | 济南大学 | MnO with magnesium-aluminum composite oxide as carrier x High-efficiency ultralow-temperature denitration catalyst |
-
2023
- 2023-11-13 CN CN202311508800.XA patent/CN117504579B/en active Active
Patent Citations (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007205304A (en) * | 2006-02-03 | 2007-08-16 | Hino Motors Ltd | Desulfurization control method for exhaust emission control device |
| CN101422689A (en) * | 2007-11-02 | 2009-05-06 | 中国科学院过程工程研究所 | Flue gas denitration method and device by storing and reducing nitrogen oxides in circulating fluid bed |
| CN101507923A (en) * | 2009-03-24 | 2009-08-19 | 中国科学院过程工程研究所 | Preparation method of catalyst for sintering flue gas and desulfurizing and denitrifying |
| CN101874964A (en) * | 2009-12-11 | 2010-11-03 | 北京科技大学 | Low temperature storage and reduction method for purifying oxynitrides |
| CN102188904A (en) * | 2011-05-11 | 2011-09-21 | 宝钢工程技术集团有限公司 | Denitration system and method for sintering flue gas without ammonia reducing agent |
| CN104667715A (en) * | 2015-02-10 | 2015-06-03 | 南京工业大学 | Flue gas desulfurization and denitrification and dust removal integrated device and process |
| CN104958978A (en) * | 2015-06-10 | 2015-10-07 | 浙江菲达脱硫工程有限公司 | Glass kiln desulfurization, denitration and dust removal apparatus and method thereof |
| CN205073858U (en) * | 2015-10-09 | 2016-03-09 | 广州特种承压设备检测研究院 | DeNOx systems is united with oxidation to reduction |
| CN105457486A (en) * | 2015-11-24 | 2016-04-06 | 西安航天源动力工程有限公司 | Coke oven flue gas integrated treatment method |
| CN106925113A (en) * | 2015-12-29 | 2017-07-07 | 烟台大学 | A kind of dust-removal and desulfurizing denitration flue gas purifying technique |
| CN208356476U (en) * | 2018-05-29 | 2019-01-11 | 北京皓天百能环保工程有限公司 | A kind of low-temperature flue gas redox denitrating system |
| CN109806764A (en) * | 2019-03-25 | 2019-05-28 | 中国科学院过程工程研究所 | A kind of industrial smoke storage reduction denitrating system and method |
| WO2020192114A1 (en) * | 2019-03-25 | 2020-10-01 | 中国科学院过程工程研究所 | Industrial flue-gas storage reduction and denitration system and method |
| CN113828148A (en) * | 2020-06-23 | 2021-12-24 | 中冶长天国际工程有限责任公司 | Flue gas treatment system and flue gas treatment method for efficiently utilizing carbon monoxide |
| CN114887618A (en) * | 2022-05-10 | 2022-08-12 | 济南大学 | MnO with magnesium-aluminum composite oxide as carrier x High-efficiency ultralow-temperature denitration catalyst |
Non-Patent Citations (1)
| Title |
|---|
| 朱廷钰、赵瑞壮: "基于臭氧氧化的同时脱硫脱硝技术应用", 第十八届全国二氧化硫 氮氧化物 汞污染防治暨细颗粒物（ PM2.5）治理技术研讨会论文集, 31 December 2014 (2014-12-31), pages 206 - 208 * |
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